AbstractThermodynamics of solution of n-alkanes and n-alkanols in the binary sorbents composed of the liquid crystalline poly(propylene imine) dendrimer and nematic p-n-pentyloxy-p'-cyanobyphenyl has been studied by inverse gas chromatography. Dependences of the activity coefficients of the solutes on composition of the sorbents are revealed to exhibit the minimum. Thermodynamic solute – sorbent compatibility characterized by the activity coefficients of the solutes is dependent on the sorbent composition; namely, it is controlled by counterbalancing of the enthalpy or entropy factors. The non-additive mode of the solute – sorbent interaction is explained by arising of the microdomain nematic structure enclosed in the columnar structure of the dendrimer.